Simultaneously effective antifungal and insecticidal or acaricidal pesticides



3,450,818 SIMULTANEOUSLY EFFECTIVE ANTI- FUNGAL AND INSECTICIDAL OR ACARICIDAL PESTICIDES Max Pianka, St. Albans, and John Duncan Edwards,

Luton, England, assignors to The Murphy Chemical Company Limited, St. Albans, England, a British company No Drawing. Filed Apr. 22, 1965, Ser. No. 450,181 Int. Cl. A01n 9/12, 21/00; C07c 155/04 US. Cl. 424-300 14 Claims ABSTRACT OF THE DISCLOSURE Certain compounds have been found to have activity against two or more pests, particularly dissimilar fungal pathogens. These compounds are defined by the structural formulae Z is selected from the group halogenoloweralkyl groups;

X is selected from the group consisting of:

(i) the group R.R NC(S)-S where R is selected from the group consisting of hydrogen atom and alkyl groups of from 1-3 carbon atoms and R is an alkyl group of from 1-3 carbon atoms;

(ii) the group R OC(S)S, where R has the meaning defined above; and

(iii) S-quinolyloxy;

Y is selected from the group consisting of hydrogen, alkyl of from l12 carbon atoms, alkenyl of from 2-6 carbon atoms, halogenoloweralkyl, phenyl, halogenophenyl, nitrophenyl, R.R N C(S) S loweralkyl-, where R and R have the meanings defined above, R OC(S)S-lower alkyl, where R has the meaning defined above, alkoxy of from 1*12 carbon atoms, halogenoalkoxy of from 1-12 carbon atoms, furyl and loweralkoxyphenyl groups, and

D is a loweralkylene bisdithiocarbamoyl group.

consisting of hydrogen and The compounds of Formulae I and II can be formulated for use in any desired way. Generally such formulations will include the pesticidal compound in association with a suitable carrier or diluent. Such carriers may be liquid or sold and designed to aid the application of the pesticide either by way of dispersing it where it is to be applied or to provide a formulation which can be made by the user into a dispersible preparation.

Liquid preparations thus particularly include preparations of the pesticide in the form of solutions, suspensions or emulsions which can be used on their own or be adapted to be made up with water or other diluents to form sprays etc.; in such cases the carrier is water or a solvent or emulsion base non-phytotoxic under the conditions of use. Generally such preparation will include a wetting, dispersing or emulsifying agent. Other liquid preparations include aerosols in which the pesticide is associated with a liquid carrier or propellant.

Solid preparations include dusts and wettable powders, granulates and pellets, and semi-solid preparations such as pastes. Such preparations may include inert solid or liquid diluents such as clays, which may themselves have wetting properties, and/ or wetting, dispersing or emulsifynited States Patent m 3,450,818 Patented June 17, 1969 ing agents; binding and/or adhesive agents may also be This invention is concerned with improvements in or relating to pesticides.

Pesticides are known for the control of fungal pathogens of similar type but when treating fungi of a dissimilar nature simultaneously it is frequently necessary either to use a mixture of appropriate fungicides or to treat the fungi separately. Likewise similar problems arise in combatting a fungus disease simultaneously with insects or aphids. For example, in horticulture it is desirable to be able to treat simultaneously apple scab and powdery mildew on apple trees but with known fungicides this is not possible or is ineflficient.

It is, therefore, an object of the invention to provide novel pesticides having activity, in general, against two or more pests, particularly dissimilar fungal pathogens, some of which pesticides have a broad spectrum of activity against fungal pathogens.

It is also an object of the invention to provide compositions having activity against fungi which attacks seeds, particularly of cereals and of sugar beet, and which are thus important as seed dressing compositions.

According to the invention, therefore, there is provided a pesticidal composition comprising an effective amount of a compound of the general formula:

| Z-OH-NI-I-C O-Y (II) in which:

Z is an hydrogen atom, or a halogenalkyl group; X has one of the following meanings:

(i) a substituted dithiocarbamoyl group of the formula R.R NC(S)S- where R is a hydrogen atom or an alkyl group containing 1-3 carbon atoms and R is an alkyl group containing 1-3 carbon atoms;

(ii) the group R OC(S)S, where R has the meaning defined above;

(iii) an 8-quinolyloxy group;

Y is a hydrogen atom, alkyl, alkenyl, halogenoalkvl.

phenyl, halogenophenyl, nitrophenyl,

where R and R have the meanings defined above, R OC(S)S-alkyl, where R has the meaning defined above, alkoxy, halogenoalkoxy, furyl or alkoxyphenyl group and D is an alkylene bisdithiocarbamoyl group.

The group Z in the above general formula is preferably hydrogen or a trihalogenomethyl group e.g. trichloromethyl or tribromomethyl.

The group D in Formula 11 above may be ethylene bisdithiocarbamoyl ize. the group The group Y may be an alkoxy group, particularly one containing 1-6 carbon atoms, a substituted dithiocarbamoyl alkyl group (i.e. the group R.R N-C(S)S-alkyl where R and R are as defined above) or the group R OC(S)-C-alkyl, where R is as defined above. Y may also be a phenyl group substituted with one or more halogen (e.g. chlorine) atoms or with one or more nitro or alkoxy groups, particularly in the ortho and/or para positions. Other examples of Y include alkenyl groups e.g. vinyl, propenyl and allyl.

The term alkyl as used herein preferably indicates that the group in question contains 1-12 carbon atoms and the term alkenyl as used herein preferably indicates that the group in question contains 2-6 carbon atoms.

The compounds of general Formulae I and II may be prepared by known general methods. In one convenient method for the preparation of various compounds of Formula I, a compound of the general formula where Z, and Y have the meanings defined above and Hal is a chlorine, bromine or iodine atom) is condensed with a salt of the formula MX, where X has the meaning defined above and M is an alkali metal or an ammonium group. Compounds of Formula II may be prepared in an analogous manner using salts of the formula M D, where D and M have the meanings defined above.

The reaction is preferably carried out in acetone or aqueous acetone. Thus, for example, the compound of Formula III can be dissolved in acetone and added to the salt MX dissolved in water, preferably with stirring at temperature between -60 and +40 C. In general, we prefer to operate at lower temperatures to avoid side reactions.

The compounds of Formulae I and II can be formulated for use in any desired way. Generally such formulations will include the pesticidal compound in association with a suitable carrier or diluent. Such carriers may be liquid or solid and designed to aid the application of the pesticide either by way of dispersing it where it is to be applied or to provide a formulation which can be made by the user into a dispersible preparation.

Liquid preparations thus particularly include preparations of the pesticide in the form of solutions, suspensions or emulsions which can be used on their own or be adapted to be made up with water or other diluents to form sprays etc.; in such cases the carrier is water or a solvent or emulsion base non-phytotoxic under the conditions of use. Generally such preparation will include a wetting, dispersing or emulsifying agent. Other liquid preparations include aerosols in which the pesticide is associated with a liqud carrer or propellant.

Solid preparations include dusts and wettable powders, granulates and pellets, and semi-solid preparations such as pastes. Such preparations may include inert solid or liquid diluents such as clays, which may themselves have wetting properties, and/or wetting, dispersing or emulsi'fying agents; binding and/or adhesive agents may also be included. Solid prepaartions also include thermal fumigating compositions wherein the pesticide is associated with a solid pyrotechnic component.

The pesticide may be used in admixture with other pesticides e.g. other fungicides so as to obtain a product having a wider spectrum of activity.

In order that the invention may be well understood thei following examples are given by way of illustration on y:

EXAMPLE 1 Methyl carbamate (9.8 g.), anhydrous chloral (19.6 g.) and fuming hydrochloric acid cc.) were mixed together. A vigorous reaction ensued and the mixture rapidly became solid. The resulting N-(1-hydroxy-2,2,2- trichloroethyl) methyl carbamate was filtered, washed with water, dried and then refluxed with thionyl chloride cc.) for 2.5 hours. The excess thionyl chloride was evaporated under reduced pressure, and the residue re EXAMPLE 2 N- l-(N'N'-dimethyl-dithiocarbamoyl)-2,2,2 trichloroethyl]-ethyl carbamate M.P. 112-114 C. (Found: Cl, 31.4%. C H Cl N O S requires Cl, 3 2.1%.) The evaluation of the LD of this product against Venturia resulted in a binodal curve at 3, 11 and 36 parts per million. The product had an LD against F usarium bulbigenum of 43 parts per million.

EXAMPLE 3 N-[1-(N'N'-dimethyl-dithiocarbamoyl)-2,2,2 trichloroethyll-n-butyl carbamate, M.P. 90-93 C. (Found: Cl, 28.7%. C H Cl N O S requires: C1, 29.0%.) It showed a binodal curve with LD of 2, 6, 16 parts per million against Venturia; an LD of 46 p.p.m. against Botrytis cinerea; and 56 p.p.m. against Cercospora melonis.

EXAMPLE 4 N [1 (N'N dimethyl dithiocarbamoyl) 2,2,2- trichloroethyl] n-hexyl carbamate, M.P. 955-96 C. Its LD against Venturia was 22 p.p.m. The compound was also active against powdery mildew (when tested by the technique described in Example 5 against Erysiphe cichoracearum it gave 80% protection from the infection).

EXAMPLE 5 N [1 (NN' dimethyldithiocarbamoyl) 2,2,2 trichloroethyl] n-dodecyl carbamate, M.P. 70-71 C. (Found: CI, 22.9%. C H C1 N O S requires Cl, 22.2%.)

' Its LD against Venturia was 2.5 p.p.m.

The product was formulated as a 5% dust by grinding with china clay percent of which is sufliciently fine to pass through a sieve containing 300 meshes to the inch).

Its efiiciency against Erysiphe cichoracearum was determined by dusting cucumber plants at the rate of 28 lbs. per acre with a wettable powder and thereafter blowing spores of cucumber mildew onto the plants. On assessment of the infection, 98% protection from infection was obtained.

EXAMPLE 6 N [1 (N'N dimethyl dithiocarbamoyl) 2,2,2- trichloroethyl]B-chloroethyl carbamate M.P. 112-113 C. (Found: Cl, C3H12C14N202S2 requires: C1, The product had an LD against Venturia of about 10 p.p.m.

EXAMPLE 7 N-(1,2,2,2-tetrachloroethyl) ethyl carbamate (22.3 g.) and sodium methyl dithiocarbamate (12.9 g.) were refluxed in acetone cc.) for 3 hours. The mixture was filtered from precipitated sodium chloride. The acetone was evaporated from the filtrate and the solid residue, N [1 (N' methyldithiocarbamoyl) 2,2,2 trichloroethyl]ethyl carbamate, was recrystallised from benzene, M.P. 144 C. (weight 13.1 g.). The LD against Venturia was 42 p.p.m.

EXAMPLE 8 Using N-(1,2,2,2-tetrachloroethyl) n-butyl carbamate (12.9 g.) and sodium methyl dithiocarbamate (8.6 g.) in acetone (80 cc.) and conditions as described in Example To a solution of N-(1,2,2,2-tetrachloroethyl)ethyl carbamate (28.5 g.) in acetone (50 cc.) was added a solution of sodium diethyl dithiocarbamate (22.5 g.) in water (30 cc.) with vigorous stirring below 37 C. Stirring was maintained at room temperature for 2 hours. An excess of water was added and the solids, N-[1-(N'N'-diethyldithiocarbamoyl) 2,2,2 trichloroethyl]ethyl carbamate, which separated out was filtered, dried, and recrystallized from a mixture of benzene and light petroleum M.P. 94-95 C. (Found: Cl, 28.9%. C10H17Cl N2O S2 re quires CI, 28.9%.) This product gave a 99% kill of aphids at 0.1% of toxicant. The product was also active against Erysiphe cichoracearum.

EXAMPLE 10 Example 9 was repeated except that in place of sodium diethyl dithiocarbamate there was used potassium xanthate. The product N-(l-xanthyl-2,2,2-trichloroethy1) ethyl carbamate was recrystallized from light petroleum M.P. 77.5-78 C. This product gave 100% kill of greenhouse red spider at 0.2% of toxicant and was also active against Venturia.

EXAMPLE 11 Forrnamide (4.5 g.) and anhydrous chloral (14.7 g.) were mixed and heated at 100 C. for 20 mins. The resultant N (1 hydroxy 2,2,2-trichloroethyl)-formamide was refluxed with thionyl chloride, in proportions of 1 mol. of the formamide derivative to 1.2 mol. of thionyl chloride, for 30 mins. A little light petroleum was then added and the excess of thionyl chloride and light petroleum was removed under reduced pressure. The resulting N- 1,2,2,2-tetrachloroethyl) -formamide was recrystallized from light petroleum M.P. 98.5100 C.

The compound (3.7 g.), dissolved in acetone (25 cc.), was added, with vigorous stirring, to a solution of sodium dimethyl dithiocarbamate (2.5 H (2.5 g.) in water (10 cc.). After 2 hours the precipitated solid was filtered off and recrystallized from methanol and acetone. N-[l- (N'N' dimethyldithiocarbamoyl) 2,2,2 trichloroethyl] formamide had M.P. 162 C. (Found: Cl, 31.6%. C H Cl N OS requires Cl, 36.0%.) The LD of this compound against Venturia was 4 p.p.m. When tested by the technique described in Example 5 against Erysz'phe cichoracearum it gave 95% protection from infection.

The products of Examples 12-22 were prepared using the general method of Example 11.

EXAMPLE 12 N [1 (NN dimethyldithiocarbamoyl) 2,2,2 trichloroethyl1acetamide, M.P. 157 C. (from benzene). (Found: Cl, 33.6%. C H Cl N OS requires Cl, 34.4%.) Its LD against Venturia was 3.4 p.p.m. When tested by the technique described in Example 5 against Erysiphe cichoracearum 85% protection from infection was obtained.

EXAMPLE 13 N [1 (N'N' dimethyldithiocarbamoyl) 2,2,2 trichloroethyl]propionamide, M.P. 179.5 C. The LD against Venturia was 19 p.p.m.

EXAMPLE 14 N [1 (N'N' dimethyldithiocarbamoyl) 2,2,2 trichloroethyl]isobutyramide, M.P. 184 C. (from benene). (Found: Cl, 31.3% C H Cl N OS requires Cl, 31.5%.) The LD of this compound against Venturia was p.p.m.

EXAMPLE N [1 (NN' dimethyldithiocarbamoyl) 2,2,2 trichloroethylJacrylamide, M.P. 193 C. (from acetone). The LD against Venturia was 3.6 p.p.m. and against Fusarium it was lower than 10 p.p.m.

EXAMPLE 16 N [1 (NN dimethyldithiocarbamoyl) 2,2,2 trichloroethyl]crotonamide, M.P. 173.5 C. (from methanol). The LD against Venturia was 2.5 p.p.m.

EXAMPLE 17 N [1 (NN' dimethyldithiocarbamoyl)) 2,2,2- trichloroethyl]-benzamide, M.P. 146147 C. This product showed a bimodal curve against Venturia with LD values of 9, 18, 30 p.p.m. 70% protection against powdery mildew was obtained by the technique of Example 5.

EXAMPLE 18 N [1 (N'N' dimethyldithiocarbamoyl) 2,2,2- trichloroethyl]-p-nitrobenzamide, M.P. 158 C. (from a mixture of ether and acetone). This product showed a binodal curve against Venturia with LD of 4, 10, 20 p.p.m. Also active against Botrytis and Cercospora (LD against the latter two was 100 p.p.m.

EXAMPLE 19 N [l (N'N' dimethyldithiocarbamoyl) 2,2,2- trichloroethyl]furoamide, M.P. 134-135 C. (from car.- bon tetrachloride). (Found: Cl, 30.5%. C H Cl N O S requires Cl, 30.8%.) This product showed a bimodal curve against Venturia with LD of 2, 13, 20 p.p.m. When tested by the technique of Example 5 it gave protection from infection against powdery mildew.

EXAMPLE 20 N [1 (N'N dimethyldithiocarbamoyl) 2,2,2- trichloroethyl]-fiuoroacetamide, M.P. 131133 C. (from isopropanol). (Found: N, 8.15%. CqHmClgFNgOSg requires N, 8.55%.) This compound had an LD against Venturia of 2.5 p.p.m. It was made up as follows: 12.5 parts of the product, 80.5 parts of china clay (95 percent of which is sufficiently fine to pass through a sieve containing 300 meshes to the inch) were ground intimately and to this was added 7 parts of sulphite lye powder and the whole mixed intimately.

This 12.5 wettable powder was diluted with water to contain 0.0125 of the toxicant. Apple rootstocks were sprayed to run-01f with this mixture. After several hours the deposit was dry. On the same day the rootstocks were placed in an infection chamber and the upper surfaces of the leaves were sprayed with a suspension containing approx. 300,000 spores of Venturia inaequalis per cc. After 48 hours, the rootstocks were removed from the infection chamber and placed in a greenhouse under artificial illumination. The infection incidence was then assessed after 21 days when it was found that there was control of the infection. When a 12.5% wettable powder of captan .(N-trichloromethyl mercapto-4-cyclohexane-1,2-dicarboximide) was diluted with water to contain 0.0125 of the toxicant and used as above, only 85% protection was obtained.

This compound, in addition to its activity against Venturia, was very efficient as a systemic aphicide. It was added to a culture solution so as to give a concentration of 0.0025% and broad beans were grown in the culture solution. A complete kill of aphids was obtained on the leaves and stems of the plants after 48 hours. It also gave, after 48 hours, 100% kill of aphids present on the leaves of broad beans when drops of a 2% solution of this compound were placed at the base of the stern of the bean plants. The plants were reinfested and 100% kill was obtained up to 6 days. This compound proved to have a low mammalian toxicity. It had an acute oral LD of 830 mg./kg. on male mice and 350 mg/kg. on male rats.

Venturia with LD values of 3, 10, 22 p.p.m. It had an LD against Cercospora melom's of 50 p.p.m. It was also active against Botrytis (96% protection using 0.065% toxicant according to Example 24) and Uromyces fabae.

EXAMPLE 22 N [1 (N'N' dimethyldithiocarbamoyl) 2,2,2- trichloroethyl]-o-amyloxybenzamide, M.P. 99101 C. (Found: N, 5.87%. C H Cl N O S requires N, 6.1.) It had good activity against Venturia.

EXAMPLE 23 Bromal and formamide were condensed as described in Example 11. The resulting N-(l-hydroxy-2,2,2-tribromoethyl)-formamide was then reacted with thionyl chloride to yield N (1 chloro 2,2,2 tribromoethyl)- formamide, which was condensed (as in Example 11) with sodium dimethyl dithiocarbamate. N-[1-(N'N'-dimethyldithiocarbamoyl) 2,2,2 tribromoethyl] formamide was recrystallized from ethanol, M.P. 137138 C. The product showed an LD against Venturia of 10 p.p.m. and against Cercospora melonis of 37 p.p.m.

EXAMPLE 24 To a solution of 8-hydroxyquinoline (77.7 g.) and N- (l,2,2,2 tetrachloroethyl) formarnide (113 g.) in acetone .(400 cc.) was added a solution of sodium hydroxide (23 g.) in water all at once. The mixture was stirred vigorously for 2 hours, and the precipitated solid was filtered, washed thoroughly with water and dried in vacuo. Weight of N [1 (8 quinolyloxy) 2,2,2 trichloroethyllformamide was 77.5 g., M.P. 168 C. (with decomposition). (Found: C1, 33.7%. C H Cl N O requires Cl, 33.1%.) It had the following LD values: against Venturia 4 p.p.m., against Fusarium 9 p.p.m. and against Cercospora 1.5 p.p.m.

This compound was formulated as described in Example 20 and diluted with water to give 0.05% concentration of toxicant. Broad bean plants were sprayed with this dilution, small discs of diameter were cut from the leaves, placed in petri dishes on moist filter paper and sprayed with a suspension containing approximately 100,- 000 spores Botrytis fabae per cc. The incidence of infection was assessed after 21 hours of incubation when it was found that 100% protection from infection was obtained.

EXAMPLE 25 N-methylol-acetamide (obtained from 5.9 g. of acetamide and formaldehyde), (in 10 cc. of benzene) was treated with thionyl chloride (10.8 cc.). The reaction mixture was heated for 2 hours on the steam bath, then set aside at room temperature for 16 hours. The solvent and excess of thionyl chloride were removed in vacuo. The chloromethyl acetarnide was dissolved in acetone (15 cc.). To this solution was added a hot solution of sodium dimethyl dithiocarbamate (2.5 H (18.8 g.) in acetone (160 cc.). Heating was discontinued and the reaction mixture stirred for 4 hours at room temperature. The solid was filtered off. The solvent was stripped from the filtrate. Water was added to the residue and the solid, N-(N',N'- dimethyldithiocarbamoyl-methyl)- acetamide, which separated was filtered off, dried in a desiccator and recrystallized from ethanol, M.P. 110 C. It had LD of p.p.m. against Venturia and gave 95% protection against powdery mildew by the technique of Example 5.

The compounds of Examples 26-28 were prepared by the method of Example 25.

EXAM'PLE 26 N- (dimethyldithiocarbamoyl-methyl)-a-chloroacetam- 8 ide, M.P. 86-88 C. Found: N, 12.7%. C H ON S CI requires N, 12.3%).

EXAMPLE 27 N-(dimethyldithiocarbamoylmethyl) a-fiuoroacetamide M.P. 77 77.s 0. (Found: N, 12.9%. CGHHFNZOSZ requires N, 13.3%).

It had an acute oral LD of 128 mg./kg. to male mice. It is therefore much less toxic than fluoroacetamide which had an LD of 15 mg./kg. It had an LD of 2 p.p.m. against Venturia. In addition to its activity against Venturia, it was also an effective systemic aphicide when tested on sugar beet, on bean plants and on big bud mite of black currants. It also gave 92% protection against powdery mildew by the technique of Example 5.

EXAMPLE 28 N- dimethyldithiocarbamoylmethyl -crotonamide. This was found to be an oil having an LD of 20 p.p.m. against Venturia and was active against powdery mildew; using the technique of Example 5 it gave 90% protection.

EXAMPLE 29 A mixture of N-[1-(N,N'-dimethyldithiocarbamoyl)- 2,2,2-trichloroethyl]chloroacetamide (6.82 g.) and an equivalent amount of sodium dimethyldithiocarbamate (2.5 H 0) in acetone cc.) was stirred for 2.5 hours. The mixture was then set aside for 2 days at room temperature, the solid filtered off and washed well with water. It was then recrystallized from ethanol. N-[1-(N,N-di methyldithiocarbamoyl-2,2,2-trichloroethyl] N",N" dimethyldithiocarbamoyl-acetamide had M.P. 146 C. (Found: Cl, 24.6%; N, 9.5%. C H Cl ON S requires Cl, 24.8%; N, 9.8%.)

This product was formulated as described in Example 20 and its efficiency against apple scab was determined as described there. It was somewhat superior to captan in its protection against the infection of scab. This compound was also formulated as a 5% dust as described in Example 5. When tested against powdery mildew on cucumbers by the technique described in Example 5, an efiiciency of control of the infection of 70% was obtained. It was also active vs. Botrytis fabae (0.065% of toxicant gave 90% control of infection by the technique of Example 24) and Uromyces fabae (broad bean rust).

EXAMPLE 30 Using similar conditions to Example 29 but employing potassium ethyl xanthate (3.22 g.) N-[1(N'N'-dimethyldithiocarbamoyl) 2,2,2-trichloroethyl]xanthylac etamide was obtained, M.P. 136 C. (with decomposition) (from isopropanol). (Found: Cl, 24.3%. C10H15C13N202S4 requires Cl, It had an LD95 of 1.5 p.p.m. against Venturia, 95 p.p.m. against Botrytis cinerea and 85 p.p.m. against Cercospora melonis.

EXAMPLE 31 To a solution of N-(1,2,2,2-tetrachloroethyl)-fluoroacetamide (12.15 g.) (prepared by the method described in Example 11) in acetone (80 cc.) was added a solution of sodium ethylene bis-dithiocarbamate (6.4 g.) in water (40 cc.) at about 60 C. with vigorous stirring. The cooling was removed and stirring continued for a further hour. On stripping the solvents a solid precipitated which was filtered off, washed with water and dried. The solid was recrystallized from acetone. Ethylene bis[S-1-(fiuoroacetamido 2,2,2-trichlor0)-ethyl]dithiocarbamate had M.P. 200 C. (with decomposition). (Found: N, 8.89%. C12H14C1F2N402S4 requires N,

This product was formulated as a wettable powder as described in Example 20. When tested by the same technique against apple scab on rootstocks it proved to have a somewhat higher efiiciency than captan (at 0.025% it gave 99% protection from infection, captan gave 95% protection). In addition this product proved to be active EXAMPLE 32 Methylol chloroacetamide (61.7 g.) and thionyl chloride (53.9 cc.) were warmed until the evolution of hydrogen chloride and sulphur dioxide subsided. The excess of thionyl chloride was removed under reduced pressure. The crude chloromethyl a-chloroacetamide (1 equivalent) dissolved in acetone (200 cc.) was added during 15 mins. to a well-stirred solution of sodium dimethyldithiocarbamate (2.5 H (188 g.; 2 equivalents) in refluxing acetone. After 1.75 hours the hot reaction mixture was filtered and the filtrate allowed to cool. The solid which separated was filtered off and recrystallized from acetone. N (dimethyldithiocarbamoylmethyl) dimethyl-dithiocarbamoylacetamide had M.P. 163164 C. (with decomposition). Found: N, 13.7%. C9H17N3OS4 requires N, 13.5%). It had an LD of 3 p.p.m. against Venturia, and was also active against Uromyces fabae.

EXAMPLE 33 Ethylene bis [S-(N-fluoroacetamido)-methyl]-dithiocarbamate prepared by the general method of Example 31 had M.-P. 180 C. (with decomposition). (Found: N, 14.5%. C H F N O S requires N, 14.4%.) In addition to its fungicidal .activity, it also gave 100% kill of aphids at 0.025% concentration. It was also very active against big bud mite of black currants.

EXAMPLE 34 N-(dimethyl-dithiocarbamoyl 4 methyl)-p-chlorobenzamide was prepared using the general method of Example 27. On recrystallization from alcohol it had M.P. 220 C. (Found: N, 9.3%, C H 'ClN OS requires N, 9.7%.)

EXAMPLE 35 N (1 dimethyldithiocarbamoyl 2,2,2-trichloroethyl) lauramide, a white crystallise solid, M.P. 108 C. (Found: N, 6.2, C17H31Cl3N2OS2 requires N, 6.2%) was prepared by the general method of Example 11. It was active against Ustilago maydis (maize smut) as well as Pseudomonas medicaginis (a bacterium).

Many of the compounds according to the invention have shown activity in in vitro tests against fungal pathogens affecting seeds and seedlings.

The test substances were evaluated by means of cupplate assay against the pathogens listed below. The criterion for activity demands that .a solution containing 200 ,ug./ml. must give a zone of inhibition mm. or more in diameter in the cup-plate assay. All substances were tested at two concentrations (200 g/ml. and 20 g/ml.) and, whenever possible, they were used in aqueous solution. For those which are insoluble in water, 50% acetone is the second solvent of choice since it has little or no effect on the test organisms but in some cases, 50% N,N- dimethylformamide was used. In order that solvent effects could be assessed on each occasion, cups containing the solvents alone were included on every plate.

Organisms .and groups Group 1:

Ustilago nua'a Group 2:

Ustilwgo avenue Helminthosporium gramineum Helminthosporium avenae Ustilago hordei Ustilago ko lleri Tilletia caries Group 3:

Fusarium culmorum Fusarium graminearum Fusarium m'vale 10 Group 4:

Phoma befae Group 5:

Xamhomonas malvacearum Group 6:

Ophiobolus gramim's The organism of Group 1 is resistant to attack by mercury and is, therefore, difficult to control.

The organisms of Group 2 can be controlled by mercury but it is important to have available non-mercurial fungicides which control these organisms owing to the growing unpopularity of mercurial fungicides. The organisms of Groups 2, 3 .and 6 are commercially significant in cereal production.

Phoma betae, the organism of Group 4, is a particularly significant fungal pathogen in sugar beet seeds the latter scarcely ever being free of contamination by this fungus.

The organism of Group 5 produces the commercial black arm of cotton and is a significant factor in the production of cotton.

The results obtained are shown in the following table:

Groups Example No. 1

A=aetive, N=n0t active.

We claim:

1. A pesticidal composition comprising a carrier containing an effective simultaneously antifungal and insecticidal or acaricidal amount of a compound selected from the group consisting of N-[l-(NN'diethyldithiocarbamoyl)-2,2,2-trichloroethyl] ethyl carbamate, N-(lxanthyl-2,2,2-trichloroethyl) ethyl carbamate, N-[1-N'N'- dimethyldithiocarbamoyl) 2,2,2 trichloroethyl]-fluoroacetamide, N-(dimethyldithiocarbamoylmethyl)-u-fluoroacetamide, ethylene bis-[S-1-(fluoroacetamido-2,2,2-trichloro)-ethyl] dithiocarbamate and ethylene bis-[S-(N- fiuoroacetamido)-methyl]-dithiocarbamate.

2. A composition as claimed in claim 1 in which said compound is N-[1-(N'N'-diethylclithiocarbamoyl)-2,2,2- trichloroethyl] ethyl carbamate.

3. A composition as claimed in claim 1 in which said compound is N-(1-xanthyl-2,2,2-trichloroethyl) ethyl car- "bama-te.

4. A composition as claimed in claim 1 in which said compound is N-[1-NN'-dimethyldithiocarbamoyl)-2,2,2- trichloroethyl]-fiuoroacetamide.

5. A composition as claimed in claim 1 in which said compound is N (dimethyldithiocarb-amoylmethyl) ovfluoroacetamide.

6. A composition as claimed in claim 1 in which said compound is ethylene bis-[S-l-(fluoroacetamido-2,2,2- trichloro)-ethyl] dithiocarbamate.

7. A composition as claimed in claim 1 in which said compound is ethylene bis-[S-(N-fiuoroacetamido)-methyl]-dithiocarbamate.

8. A method of simultaneously protecting plants against damage by both types of pests, fungal pathogens and insects or acarids which comprises contacting said pests with an effective amount of a compound selected from the group consisting of N-[l-(NN'-diethyldithiocarbamoyl)-2,2,2-trichloroethyl] ethyl carbamate, N-(l- Xanthyl 2,2,2 trichloroethyl) ethyl carbamate, N-[l- NN-dimethyldithiocarbamoyl) 2,2,2 trichloroethyl]- fluoroacetamide, N-(dimethyldithiocarbamoylmethyl)-afluoroacetamide, ethylene bis [S 1 (fluoroacetamido- 2,2,2-trichloro)-ethyl] dithiocarbamate and ethylene bis- [S- (N-fluoroacetarnido -methyl] -dithiocarb amate.

9. A method as claimed in claim 8 in which said pests are contacted with N-[1-(N'N'-diethyldithiocarbamoyl)- 2,2,2-trichloroethyl] ethyl carbamate.

10. A method as claimed in claim 8 in which said pests are contacted with N-(1-xanthyl-2,2,2-trichloroethyl) ethyl carbamate.

11. A method as claimed in claim 8 in which said pests are contacted With N-[l-NN-dimethyldithiocarbamoyl)- 2,2,2-trichloroethyl]-fluoroacetamide.

12. A method as claimed in claim 8 in which said pests are contacted with N-(dimethyldithiocarbamoylmethyl)- a-fiuoroacetamide.

13. A method as claimed in claim 8 in which said pests are contacted with ethylene bis-[S-l-(fluoroacetamido- 2,2,2-trichloro)-ethyl] dithiocarbamate.

14. A method as claimed in claim 8 in which said pests are contacted with ethylene bis-[S-(N-fluoroacetamido)- methyl] -dithiocarbamate.

References Cited UNITED STATES PATENTS 3,056,789 10/1962 Urech 260--287 X 3,125,598 3/1964 Kuhle et a1 260287 X 3,245,997 4/1966 Yonan 260-288 3,308,128 371967 Robinson 260-288 LEWIS GOTTS, Primary Examiner.

S. K. ROSE, Assistant Examiner.

US. Cl. X.R. 

